CN114380691B - Method for reducing acid value and chromaticity in benzyl benzoate by using composite filler system - Google Patents
Method for reducing acid value and chromaticity in benzyl benzoate by using composite filler system Download PDFInfo
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- CN114380691B CN114380691B CN202210056336.4A CN202210056336A CN114380691B CN 114380691 B CN114380691 B CN 114380691B CN 202210056336 A CN202210056336 A CN 202210056336A CN 114380691 B CN114380691 B CN 114380691B
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- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 title claims abstract description 258
- 229960002903 benzyl benzoate Drugs 0.000 title claims abstract description 129
- 239000002253 acid Substances 0.000 title claims abstract description 95
- 239000000945 filler Substances 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 74
- 230000008569 process Effects 0.000 claims abstract description 31
- 238000005070 sampling Methods 0.000 claims abstract description 23
- 238000011282 treatment Methods 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000006004 Quartz sand Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 42
- 238000012360 testing method Methods 0.000 description 16
- 230000006872 improvement Effects 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004042 decolorization Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 235000013599 spices Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 235000007173 Abies balsamea Nutrition 0.000 description 2
- 239000004857 Balsam Substances 0.000 description 2
- 244000018716 Impatiens biflora Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JHGWQSGWUPCKNT-UHFFFAOYSA-N 2-tert-butyl-4-methyl-1,3,5-trinitrobenzene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C(C)(C)C)=C1[N+]([O-])=O JHGWQSGWUPCKNT-UHFFFAOYSA-N 0.000 description 1
- 244000144725 Amygdalus communis Species 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 240000006497 Dianthus caryophyllus Species 0.000 description 1
- 235000009355 Dianthus caryophyllus Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 244000014047 Polianthes tuberosa Species 0.000 description 1
- 235000016067 Polianthes tuberosa Nutrition 0.000 description 1
- 241000722923 Tulipa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention provides a method for reducing acid value and chromaticity in benzyl benzoate by using a composite filler system. And the circulating component inputs unqualified benzyl benzoate detected by the sampling port into the corresponding unit again for circulating treatment until benzyl benzoate with qualified acid value, chromaticity and purity is obtained. The invention adopts a sectional circulation mode, avoids the condition that the whole composite filler system is passed again due to unqualified certain index of benzyl benzoate, and shortens the process time; the process is carried out at normal temperature, overcomes the defect that benzyl benzoate is decomposed again due to heating in the traditional process, is simple and easy to realize, has low cost and less pollutant generation, and has the advantages of environmental protection.
Description
Technical Field
The invention relates to the technical field of benzyl benzoate purification, in particular to a method for reducing acid value and chromaticity in benzyl benzoate by using a composite filler system, and more particularly relates to a method for efficiently reducing trace acid value and chromaticity in benzyl benzoate by using a composite filler system.
Background
Benzyl benzoate is an organic compound with a molecular formula of C 14H12O2, is colorless oily liquid, has light fragrance like almond, and is spicy. Natural benzyl benzoate is present in Peruvian balsam, tuberose, carnation and Tulipa balsam; the sodium benzoate and benzyl chloride are used as raw materials and are synthesized by a synthetic reaction. In the perfume industry, benzyl benzoate is produced by adopting an alcohol exchange method, and is prepared by alcohol exchange of ethyl benzoate and benzyl alcohol by taking sodium carbonate as a catalyst; the organic compound is mainly used as a solvent of artificial musk, vanillin and other fragrances, a fragrance fixing agent of floral-type essence, blended fragrances of ylang and other fragrances and the like.
The present industry comprises the steps of heating and reacting sodium benzyl alcohol with benzaldehyde, refining to obtain benzyl benzoate, reacting sodium benzoate with benzyl chloride, esterifying benzoic acid with benzyl alcohol, recycling and refining byproducts in the toluene air oxidation process, and the like. However, the benzyl benzoate prepared by the method has dark color, high chromaticity and acid value and contains more impurities. The purity of the benzyl benzoate after rectification and purification is greatly improved, but a small amount of air is easy to permeate in the vacuum rectification process, and the benzyl benzoate is easy to be heated and decomposed at high temperature for a long time to generate other impurities. Therefore, the benzyl benzoate obtained by vacuum rectification has high acid value and chromaticity, and can not meet the quality requirement of perfume-grade benzyl benzoate, thereby limiting the application of benzyl benzoate in high-end products.
Since benzyl benzoate is unstable in nature and is easily decomposed when heated, acid value and impurities are high, and thus industrial benzyl benzoate has more limitations and difficulties in refining and purifying to high-quality perfume-grade benzyl benzoate.
At present, when benzyl benzoate is applied to a perfume-grade high-end product, aiming at the situation that the acid value and the chromaticity are higher after the rectification process, the benzyl benzoate is usually subjected to multiple alkaline washing and water washing treatments, and then is subjected to heating, decompression and dehydration. The method has higher cost, can generate a large amount of organic wastewater, has complex operation process, and is likely to decompose again when heated and dehydrated, so that the purity and acid value of the product still do not reach the standards; or further purifying benzyl benzoate by adopting a secondary or even multiple rectification process, but the refined benzyl benzoate has burnt odor due to the fact that the retention time of high temperature is long and the like, and the color number of the product is increased. In addition, the two methods have poor treatment effect on the problem of high chroma of benzyl benzoate, and the repeated temperature rising dehydration or rectification often leads to further increase of color number of the product, increase of cost and consumption, generation of alkaline washing or rectification waste, and high environmental protection pressure.
In view of the foregoing, there is a need for an improved method for reducing acid number and color in benzyl benzoate using a composite filler system that addresses the above-described problems.
Disclosure of Invention
The invention aims to provide a method for reducing acid value and chromaticity in benzyl benzoate by using a composite filler system, wherein the composite filler system is arranged behind a product tank of a benzyl benzoate rectification process to form a seal with the rectification process, the acid value and chromaticity of a benzyl benzoate product are further reduced in a nitrogen atmosphere, and impurities are removed, so that the quality of the benzyl benzoate meets the requirements of a perfume-level high-end product; the method is carried out under the atmosphere of normal temperature nitrogen, air is isolated, the process is simple and easy to realize, the composite filler system can be recycled, the cost is low, the pollutant is less, and the method has the advantages of being green and environment-friendly.
In order to achieve the aim, the invention provides a method for reducing the acid value and the chromaticity of benzyl benzoate by using a composite filler system, wherein benzyl benzoate flows in from a feed inlet at the upper part of the composite filler system, sequentially passes through an acid removal unit, a decoloring unit and an adsorption unit of the composite filler system, and flows out from a discharge outlet at the bottom of the composite filler system; and the sampling port and the circulating component are arranged below the acid removal unit, the decoloring unit and the adsorption unit, and the circulating component inputs unqualified benzyl benzoate detected by the sampling port into the corresponding unit again for circulating treatment until benzyl benzoate with qualified quality is obtained.
As a further improvement of the present invention, the acid removal unit includes a buffer layer and an alkaline filler layer, the alkaline filler layer including an alkaline oxide and an alkaline resin.
As a further improvement of the present invention, the decolorizing unit comprises one or more of activated clay, diatomaceous earth, and macroporous resin.
As a further improvement of the present invention, the mass ratio of the basic oxide to the basic resin is 1 (0.5 to 2.0).
As a further improvement of the present invention, the basic oxide includes one or more of γ -Al 2O3, light magnesium oxide, zinc oxide, and calcium oxide.
As a further improvement of the present invention, the adsorption unit contains one or more of white carbon black, neutral silica gel and large-particle activated carbon.
As a further improvement of the invention, the decoloring unit also comprises large-particle glass sand or quartz sand which is used for dispersing materials and reducing material layer resistance.
As a further improvement of the present invention, the buffer layer contains one or more of granular activated carbon, kaolin, glass sand and quartz for uniformly dispersing the benzyl benzoate, reducing impact, and avoiding suspension of basic oxide powder.
As a further improvement of the invention, a permeable membrane is arranged between the buffer layer and the alkaline filler layer to allow the mobile phase of benzyl benzoate to pass through and to block the back mixing of the materials of the two layers.
As a further improvement of the invention, the composite filler system is arranged after a product tank of the rectifying process of benzyl benzoate, forms a seal with the rectifying process, further reduces the acid value and chromaticity of the benzyl benzoate product, and removes impurities.
The beneficial effects of the invention are as follows:
1. According to the method for reducing the acid value and the chromaticity in the benzyl benzoate by using the composite filler system, benzyl benzoate flows in from the feed inlet at the upper part of the composite filler system, sequentially passes through the acid removal unit, the decoloring unit and the adsorption unit of the composite filler system, and flows out from the discharge outlet at the bottom of the composite filler system. The sampling port and the circulating component are arranged below the acid removal unit, the decoloring unit and the adsorption unit, and the circulating component inputs unqualified benzyl benzoate detected by the sampling port into the corresponding unit again for circulating treatment until benzyl benzoate with qualified quality is obtained. The units of the composite filler system of the method are complemented with each other in function, and the acid value, chromaticity and purity of the obtained benzyl benzoate product can meet the application requirements of the high-end product of the spice grade; the method is carried out under the atmosphere of normal temperature nitrogen, air is isolated, energy consumption is reduced, the process is simple and easy to realize, the composite filler system can be recycled, the cost is low, raw material waste is avoided, the pollutant is less, and the method has the advantages of being green and environment-friendly.
2. The circulation components are arranged behind each unit of the composite filler system, benzyl benzoate is treated by adopting sectional circulation, so that benzyl benzoate is prevented from passing through the whole composite filler system again due to unqualified certain index, and the treatment time is prolonged; the arrangement shortens the whole process time and has better economic benefit. The composite filler system can be arranged behind a product tank of a rectifying process of benzyl benzoate, forms a seal with the rectifying process, isolates air, and further reduces the acid value and chromaticity of benzyl benzoate which does not meet the application requirements of spice-grade products after rectification, and removes impurities until the quality of benzyl benzoate meets the application requirements; the method is carried out in a nitrogen atmosphere at normal temperature, and overcomes the defect that benzyl benzoate is heated and cracked or oxidized and cracked due to heating in the traditional purification process.
3. The alkaline filler layer of the acid removal unit comprises alkaline oxide and alkaline resin, the alkaline oxide and the alkaline resin can effectively remove acidic substances in benzyl benzoate, and the alkaline resin has larger granularity due to the difference of the granularity of the alkaline oxide and the granularity of the alkaline resin, and can also be used for reducing the resistance of a material layer to benzyl benzoate, so that a benzyl benzoate mobile phase with larger viscosity can smoothly pass through. Activated clay, diatomite or macroporous resin adopted by the decoloring unit can adsorb trace impurities of the passing benzyl benzoate so as to reduce color number. The silicon hydroxyl on the surface of neutral silica gel in the adsorption unit can enable metal ion impurities and polar groups generated in benzyl benzoate after acid removal or contained in raw materials to be adsorbed on the surface of the neutral silica gel in a complexing mode, so that the metal ion impurities are further removed; and white carbon black and large-particle activated carbon further ensure the color number and quality of benzyl benzoate products by utilizing the better characteristic of absorbing various trace impurities.
4. The composite filler system can be recycled for multiple times, so that the production cost is reduced, and higher economic benefit is generated; after the composite filler system is saturated after long-term use treatment, the filler is treated as solid waste. Compared with the traditional method for reducing the acid value and decoloring by washing with alkali or rectifying for multiple times, the method has extremely high acid value and decoloring treatment efficiency on benzyl benzoate products, extremely low solid waste proportion generated by treating benzyl benzoate products per ton, obvious advantages and worth popularizing in more production lines.
Drawings
FIG. 1 is a schematic process diagram of the method of the present invention for reducing acid number and color in benzyl benzoate using a composite filler system.
Reference numerals
1-An acid removal unit; 11-a buffer layer; 12-an alkaline filler layer; 13-a permeable membrane; 2-decolorizing units; a 3-adsorption unit; 4-sampling ports; 5-a circulation assembly; 51-a material conveying pump; 52-a material conveying pipe; 6-rectifying a product tank; 7-a finished product storage tank.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Referring to fig. 1, the method for reducing acid value and chromaticity in benzyl benzoate by using the composite filler system provided by the invention can effectively reduce acid value, chromaticity and impurities in benzyl benzoate by using the composite filler system, so that the application requirement of a perfume-level high-end product is met. Wherein, the composite filler system sequentially comprises an acid removal unit 1, a decoloring unit 2 and an adsorption unit 3 from top to bottom. The specific principle is as follows:
Benzyl benzoate flows in from a feed inlet at the upper part of the composite filler system, flows out from a discharge outlet at the bottom of the composite filler system after passing through an acid removal unit 1, a decolorization unit 2 and an adsorption unit 3 of the composite filler system in sequence, and enters a finished product storage tank 7. Wherein, the sampling port 4 and the circulating component 5 are arranged below the acid removing unit 1, the decolorizing unit 2 and the adsorbing unit 3, and the material conveying pump 51 of the circulating component 5 is used for conveying unqualified benzyl benzoate detected by the sampling port into the corresponding unit again for circulating treatment by using the material conveying pipe 52 until benzyl benzoate with qualified quality is obtained. The units of the composite filler system of the method are complemented with each other in function, and the acid value, chromaticity and purity of the obtained benzyl benzoate product can meet the application requirements of the high-end product of the spice grade; the method is carried out under the atmosphere of normal temperature nitrogen, air is isolated, energy consumption is reduced, the process is simple and easy to realize, the composite filler system can be recycled, the cost is low, raw material waste is avoided, the pollutant is less, and the method has the advantages of being green and environment-friendly.
Particularly, the circulation assembly 5 is arranged behind each unit of the composite filler system, and the benzyl benzoate is treated by adopting sectional circulation, so that benzyl benzoate is prevented from passing through the whole composite filler system again due to unqualified certain index, and the treatment time is prolonged; the arrangement shortens the whole process time and has better economic benefit.
Referring to fig. 1, the composite filler system is further provided with an air supply system, which is respectively connected with the acid removal unit 1, the decolorizing unit 2, the adsorption unit 3 and the finished product storage tank 7, and inert gas is introduced before the composite filler system works to remove air, and internal micro positive pressure is kept when the composite filler system works to prevent air from entering, and the pressure balance of the system is maintained, so that materials can sequentially pass through the acid removal unit 1, the decolorizing unit 2 and the adsorption unit 3 from top to bottom, and the acid removal and decolorization effects of benzyl benzoate are achieved. In particular embodiments, nitrogen may be used as the inert gas.
Specifically, the acid removal unit 1 comprises a buffer layer 11 and an alkaline filler layer 12, wherein the alkaline filler layer 12 contains alkaline oxide and alkaline resin, the alkaline oxide and the alkaline resin not only can remove acidic substances in benzyl benzoate, but also can reduce the resistance of a material layer due to the difference of the granularity of the alkaline oxide and the granularity of the alkaline resin, so that a benzyl benzoate mobile phase with higher viscosity can smoothly pass through. The mass ratio of the alkaline oxide to the alkaline resin is 1 (0.5-2.0); the basic oxide includes one or more of gamma-Al 2O3, light magnesium oxide, zinc oxide and calcium oxide. The buffer layer 11 contains one or more of granular activated carbon, kaolin, glass sand and quartz for uniformly dispersing benzyl benzoate, reducing impact, and avoiding suspension of basic oxide powder.
The decoloring unit 2 comprises one or more of activated clay, diatomite and macroporous resin, and can adsorb trace impurities of benzyl benzoate passing through so as to reduce color number; the decoloring unit 2 also comprises large-particle glass sand or quartz sand which is used for dispersing materials and reducing the material layer resistance. The adsorption unit 3 comprises one or more of white carbon black, neutral silica gel and large-particle activated carbon, and the adsorption unit 3 performs final impurity removal and water absorption on benzyl benzoate to obtain benzyl benzoate with high purity.
In particular, a permeable membrane 13 is arranged between the buffer layer and the alkaline filler layer to allow the mobile phase of benzyl benzoate to pass through and separate the materials of the two layers from back mixing; because of the high viscosity of benzyl benzoate, the permeable membrane 13 can avoid benzyl benzoate from driving the solid particles of the two layers to move in a large area in the flowing process, and losing the specific effect. In addition, the composite filler system is arranged in a rectification product tank 6 of the rectification process of benzyl benzoate, forms a seal with the rectification process, further reduces the acid value and chromaticity of benzyl benzoate products, and removes impurities. The method is carried out in a nitrogen atmosphere at normal temperature, isolates air, and overcomes the defect that benzyl benzoate is decomposed again due to heating in the traditional purification process.
In a specific embodiment, two or more composite filler systems are arranged behind the rectifying product tank 6 of the rectifying process of benzyl benzoate, so that the working efficiency is improved, and when the treatment effect of the composite filler systems is poor, the composite filler systems are convenient to replace in time, so that the normal output operation of benzyl benzoate is ensured.
In a specific embodiment, when the composite filler system is designed according to the treatment capacity of 45-60 kg benzyl benzoate per hour, the total length of the filler system is 900-1100 mm, and the diameter is 300-500 mm; the thickness of the acid removing unit 1 is 150-600 mm, wherein the thickness of the buffer layer 11 is 100-300 mm, and the thickness of the alkaline filler layer 12 is 30-300 mm; the thickness of the decoloring unit 2 is 20-200 mm; the thickness of the adsorption unit 3 is 20-200 mm.
Example 1
The embodiment provides a method for reducing acid value and chromaticity in benzyl benzoate by using a composite filler system, wherein the composite filler system comprises an acid removal unit 1, a decoloring unit 2 and an adsorption unit 3 from top to bottom. The specific method comprises the following steps: benzyl benzoate after a rectification product tank 6 of the rectification process flows in from a feed inlet at the upper part of the composite filler system, sequentially passes through an acid removal unit 1, a decolorization unit 2 and an adsorption unit 3 of the composite filler system, flows out from a discharge outlet at the bottom of the composite filler system, and reaches a finished product storage tank 7 below the composite filler system.
A composite filler system for processing 50kg of benzyl benzoate per hour was designed, the diameter of the composite filler system was 400mm, and the flow rate of benzyl benzoate was controlled to ensure sufficient contact and action of benzyl benzoate with each unit. Wherein the buffer layer 11 of the acid removal unit 1 is a granular activated carbon layer with the thickness of 300mm; the alkaline filler layer 12 was an alkaline oxide (m (. Gamma. -Al 2O3): m (light magnesium oxide): m (calcium oxide) 2:1:1) and an alkaline resin, in a mass ratio of 1:2 and a thickness of 300mm. The decolorizing unit is a mixture of activated clay, diatomite and quartz sand, and has a thickness of 200mm. The adsorption unit 3 is a mixture of neutral silica gel and granular activated carbon powder, and the thickness is 200mm.
Test example 1 acid number, color and purity of benzyl benzoate in rectifying product tank 6 before entering the composite packing system; then, sampling test is carried out on sampling ports 4 below the acid removal unit 1, the decoloring unit 2 and the adsorption unit 3 respectively, and the acid value, the chromaticity and the purity of the sample are tested; the test results are shown in the following table.
Wherein, benzyl benzoate product quality standard: an acid value of <0.2; the acid value test method is as follows:
wherein: v-reagent consumes volume of standard solution, mL
C-concentration of standard solution, mol/L
M-sample weight, g
0.2122-The mass of benzyl benzoate in grams corresponds to 1.0ml of NaOH standard titration solution (C NaOH =1.000 mol/L).
Table 1 example 1 product test results
| Sampling position | Content (%) | Acid value | Chromaticity (Hazen) |
| Rectifying product tank | 99.51 | 0.22 | 30 |
| After the acid removing unit | 99.61 | 0.06 | 30 |
| After the decoloring unit | 99.64 | 0.05 | 20 |
| After the adsorption unit | 99.65 | 0.06 | 15 |
As can be seen from Table 1, after the composite filler system of the invention is adopted, not only the purity of benzyl benzoate is improved, but also the acid value of benzyl benzoate is obviously reduced, and the acid value of benzyl benzoate is obviously reduced after the acid removal unit 1, and is changed from 0.22 to 0.06, so that the acid value standard of the benzyl benzoate product is completely compounded; and the chromaticity of benzyl benzoate after the decoloring unit 2 and the adsorbing unit 3 is changed from 30 # to 15 #. The results of the example show that the method of the invention can effectively reduce the acid value of the rectified benzyl benzoate, and simultaneously has a promoting effect on the reduction of the color number of the product, so that the benzyl benzoate is more suitable for the application of the high-end product with a high spice grade.
Example 2
This example provides a method for reducing acid number and chromaticity in benzyl benzoate using a composite filler system, wherein the basic filler layer 12 is an alkaline oxide (m (gamma-Al 2O3): m (light magnesium oxide): m (calcium oxide): 1.3:1.3:1) and alkaline resin in a mass ratio of 1.5:1, and the remainder is substantially the same as example 1, and is not repeated herein.
Test example 2 acid number, color and purity of benzyl benzoate in rectifying product tank 6 before entering the composite packing system; then, sampling test is carried out on sampling ports 4 below the acid removal unit 1, the decoloring unit 2 and the adsorption unit 3 respectively, and the acid value, the chromaticity and the purity of the sample are tested; the test results are shown in the following table.
Table 2 example 2 product test results
| Sampling position | Content (%) | Acid value | Chromaticity (Hazen) |
| Rectifying product tank | 99.32 | 0.4 | 40 |
| After the acid removing unit | 99.48 | 0.14 | 40 |
| After the decoloring unit | 99.52 | 0.12 | 30 |
| After the adsorption unit | 99.51 | 0.13 | 20 |
As shown in Table 2, the composite filler system of the invention not only can improve the purity of benzyl benzoate, but also can effectively reduce the acid value of benzyl benzoate after rectification, has good effect on benzyl benzoate with higher acid value, and also has promotion effect on product color number reduction.
Comparative example 1
Comparative example 1 provides a method for reducing acid number and color in benzyl benzoate using a composite filler system that is not provided with a decolorization unit 2 as compared to example 1, and otherwise is substantially the same as in example 1 and is not described herein.
Comparative example 1 was tested for acid number, chromaticity and purity of benzyl benzoate in rectifying product tank 6 before entering the composite packing system; then, sampling and testing the sampling ports 4 below the acid removal unit 1 and the adsorption unit 3 respectively to test the acid value, chromaticity and purity of the acid removal unit and the adsorption unit; the test results are shown in the following table.
Table 3 comparative example 1 product test results
| Sampling position | Content (%) | Acid value | Chromaticity (Hazen) |
| Rectifying product tank | 99.51 | 0.22 | 30 |
| After the acid removing unit | 99.62 | 0.06 | 30 |
| After the adsorption unit | 99.66 | 0.06 | 25 |
As is clear from Table 3, the composite column without decolorizing units can effectively reduce the acid value of benzyl benzoate after rectification, but has a remarkable effect of reducing the color number of the product.
Comparative example 2
Comparative example 2 provides a method for reducing acid number and color in benzyl benzoate using a composite packing system that is not provided with adsorption unit 2 as compared to example 1, and otherwise is substantially the same as example 1 and is not described herein.
Comparative example 2 was tested for acid number, chromaticity and purity of benzyl benzoate in rectifying product tank 6 before entering the composite packing system; then, sampling and testing the sampling ports 4 below the acid removal unit 1 and the decolorizing unit 2 respectively to test the acid value, chromaticity and purity of the acid removal unit and the decolorizing unit; the test results are shown in the following table.
Table 4 comparative example 2 product test results
| Sampling position | Content (%) | Acid value | Chromaticity (Hazen) |
| Rectifying product tank | 99.51 | 0.22 | 30 |
| After the acid removing unit | 99.63 | 0.05 | 30 |
| After the decoloring unit | 99.68 | 0.06 | 20 |
As shown in Table 4, the composite column without adsorption unit can effectively reduce the acid value of benzyl benzoate after rectification, has good effect of reducing the acid value of the product, but has slightly poor transparency and clarity.
In summary, the invention provides a method for reducing acid value and chromaticity in benzyl benzoate by using a composite filler system, which flows benzyl benzoate from a feed inlet at the upper part of the composite filler system, sequentially passes through an acid removal unit, a decolorizing unit and an adsorption unit of the composite filler system, and flows out from a discharge outlet at the bottom of the composite filler system. And the material conveying pump of the circulating assembly inputs unqualified benzyl benzoate detected by the sampling port into the corresponding unit again for circulating treatment until benzyl benzoate with qualified acid value, chromaticity and purity is obtained. The invention adopts a sectional circulation mode, avoids the condition that the whole composite filler system is passed again due to unqualified certain index of benzyl benzoate, and shortens the process time; the method is carried out in a nitrogen atmosphere at normal temperature, isolates air, and overcomes the defect that benzyl benzoate is heated and cracked or oxidized and cracked due to heating in the traditional purification process. The units of the composite filler system are complemented with each other in function, and the acid value, chromaticity and purity of the obtained benzyl benzoate product can meet the application requirements of the high-end product with high spice level; and the process is simple and easy to realize, the composite filler system can be recycled, the cost is low, the waste of raw materials is avoided, the pollutant is less, and the method has the advantages of being green and environment-friendly.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (4)
1. The method for reducing the acid value and the chromaticity in the benzyl benzoate by using the composite filler system is characterized in that the method is carried out under the atmosphere of normal temperature nitrogen, the benzyl benzoate flows in from a feed inlet at the upper part of the composite filler system, and flows out from a discharge outlet at the bottom of the composite filler system after sequentially passing through an acid removal unit, a decoloring unit and an adsorption unit of the composite filler system; sampling ports and circulating components are arranged below the acid removal unit, the decoloring unit and the adsorption unit, and the circulating components re-input unqualified benzyl benzoate detected by the sampling ports into corresponding units for circulating treatment until benzyl benzoate with qualified quality is obtained;
The acid removal unit comprises a buffer layer and an alkaline filler layer, wherein the alkaline filler layer comprises alkaline oxide and alkaline resin; the decoloring unit comprises one or more of activated clay, diatomite and macroporous resin; the adsorption unit comprises one or more of white carbon black, neutral silica gel and large-particle activated carbon; the buffer layer comprises one or more of granular activated carbon, kaolin, glass sand and quartz, and is used for uniformly dispersing the benzyl benzoate, so that the impact is reduced, and the suspension of alkaline oxide powder is avoided; a permeable membrane is arranged between the buffer layer and the alkaline filler layer so as to allow the mobile phase of benzyl benzoate to pass through and separate the materials of the two layers from back mixing;
the composite filler system is arranged behind a product tank of the rectification process of benzyl benzoate, forms a seal with the rectification process, further reduces the acid value and chromaticity of the benzyl benzoate product, and removes impurities.
2. The method for reducing acid value and chromaticity in benzyl benzoate with a composite filler system as recited in claim 1, wherein the mass ratio of the basic oxide to the basic resin is 1 (0.5-2.0).
3. The method of reducing acid number and color in benzyl benzoate with a composite filler system according to claim 2, wherein the basic oxides include one or more of gamma-Al 2O3, light magnesium oxide, zinc oxide, and calcium oxide.
4. The method of reducing acid number and color in benzyl benzoate using a composite packing system according to claim 1 wherein said decolorizing unit further comprises large particle glass sand or quartz sand for dispersing materials to reduce material layer drag.
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| CN103060024A (en) * | 2012-12-28 | 2013-04-24 | 中国科学院深圳先进技术研究院 | An apparatus and a method for removing free acids in ester synthetic oils and applications of the apparatus |
| CN111574373A (en) * | 2020-06-24 | 2020-08-25 | 湖北葛店人福药用辅料有限责任公司 | Method for purifying benzyl benzoate |
| CN114405062A (en) * | 2022-01-18 | 2022-04-29 | 武汉有机实业有限公司 | Method for reducing acid value in benzaldehyde by using composite filler column |
| CN114656361A (en) * | 2022-03-30 | 2022-06-24 | 潜江新亿宏有机化工有限公司 | Continuous purification system and method for perfume-grade benzyl acetate |
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| CN106748774B (en) * | 2016-11-13 | 2020-07-24 | 中海油天津化工研究设计院有限公司 | Refining method of cyclohexane diformate plasticizer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103060024A (en) * | 2012-12-28 | 2013-04-24 | 中国科学院深圳先进技术研究院 | An apparatus and a method for removing free acids in ester synthetic oils and applications of the apparatus |
| CN111574373A (en) * | 2020-06-24 | 2020-08-25 | 湖北葛店人福药用辅料有限责任公司 | Method for purifying benzyl benzoate |
| CN114405062A (en) * | 2022-01-18 | 2022-04-29 | 武汉有机实业有限公司 | Method for reducing acid value in benzaldehyde by using composite filler column |
| CN114656361A (en) * | 2022-03-30 | 2022-06-24 | 潜江新亿宏有机化工有限公司 | Continuous purification system and method for perfume-grade benzyl acetate |
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